JP2501248B2 - Monomolecular coating object and method of manufacturing the same - Google Patents
Monomolecular coating object and method of manufacturing the sameInfo
- Publication number
- JP2501248B2 JP2501248B2 JP3024025A JP2402591A JP2501248B2 JP 2501248 B2 JP2501248 B2 JP 2501248B2 JP 3024025 A JP3024025 A JP 3024025A JP 2402591 A JP2402591 A JP 2402591A JP 2501248 B2 JP2501248 B2 JP 2501248B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- monomolecular
- base material
- chlorosilane
- sicl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Laminated Bodies (AREA)
- Silicon Compounds (AREA)
- Surgical Instruments (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属、セラミックス製
などの刃物や針などの基材表面に単分子膜を形成した物
体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an object having a monomolecular film formed on the surface of a base material such as a knife or a needle made of metal or ceramics.
【０００２】[0002]
【従来の技術】刃物の少なくとも刃部を防錆処理するこ
とは、刃物の機能を長期間保つ上で重要なことである。
すなわち刃物は錆の発生によって切れ味が大きく低下す
るからである。また針などにおいても、差し込み抵抗が
低く、防錆効果に優れたものは、医療業界において望ま
れている。2. Description of the Related Art It is important to prevent at least the blade portion of a blade from rusting in order to maintain the function of the blade for a long period of time.
That is, the sharpness of the blade greatly deteriorates due to the generation of rust. Also in needles and the like, those having a low insertion resistance and an excellent anticorrosive effect are desired in the medical industry.
【０００３】従来、刃物の切れ味を改善したり切り屑の
付着を防止する方法として、刃の表面をフッ素樹脂など
でコートする方法がある。この場合、フッ素樹脂は弗素
エナメルを薄く塗布した後、焼き付け塗装することによ
り、コーティングする手段がとられる。またそのほかの
樹脂コーティングにおいては、溶剤に溶解または懸濁さ
せた塗料を塗布して溶剤を乾燥するとか、焼き付け硬化
させる手段などが採られる。また、針などについては差
し込み抵抗を低くするためにはよく研磨すること以外知
られていない。また特開平２−２４８４８０号公報に
は、パーフロロ基と加水分解可能な有機基を含む物質を
透明基材表面に塗布してフッ化炭素基を含む塗膜を形成
することが提案されており、特開昭６０−４０２５４号
公報には、シラン化合物または合成樹脂材料からなる第
１の塗膜と、ポリフルオロ化基含有化合物からなる第２
の塗膜を形成することが提案されており、特開昭５８−
１４７４８３号公報には、ポリフルオロアルキル基含有
シラン化合物または該化合物の加水分解縮合物とシラン
カップリング剤とコロイダルシリカとからなる撥水撥油
剤が提案されている。 Conventionally, there has been a method of coating the surface of the blade with a fluororesin or the like as a method of improving the sharpness of the blade and preventing the adhesion of chips. In this case, the fluororesin may be coated by applying a thin coating of fluorine enamel and then baking coating. In addition, in other resin coating, a means of applying a coating material dissolved or suspended in a solvent and drying the solvent, or baking and curing the coating material is used. Further, with respect to needles and the like, nothing is known other than that they are well polished to reduce the insertion resistance. Also, in Japanese Patent Laid-Open No. 2-248480.
Is a substance containing a perfluoro group and a hydrolyzable organic group.
Coating on the transparent substrate surface to form a coating film containing fluorocarbon groups
It has been proposed to do so, as disclosed in JP-A-60-40254.
The publication discloses that a silane compound or a synthetic resin material
A coating film of No. 1 and a polyfluorinated group-containing compound No. 2
It has been proposed to form a coating film of
Japanese Patent No. 147483 discloses that a polyfluoroalkyl group is contained.
Silane compound or hydrolysis condensate of the compound and silane
Water and oil repellent consisting of coupling agent and colloidal silica
Agents have been proposed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、前記の
フッ素樹脂をコートする方法では、刃との密着が悪く高
耐久性の刃物が得られなかった。またコート厚みを薄く
することができなかったため、きわめて鋭利な刃物、例
えば剃刀などではフッ素樹脂でコートする方法は利用で
きなかった。また、ほかの樹脂コーティングも同様に密
着強度が弱く、耐久性に問題があるという課題があっ
た。これは刃物基材との接着力が、物理吸着によること
に起因する。また、前記特開平２−２４８４８０号公
報、特開昭６０−４０２５４号公報及び特開昭５８−１
４７４８３号公報の提案もナノメータレベルの膜厚のフ
ッ化炭素系単分子膜を形成することは困難であったの
で、刃物や針に応用することはできなかったという問題
があった。 However, in the above-mentioned method of coating a fluororesin, the adhesion to the blade is poor and a highly durable blade cannot be obtained. Further, since the coat thickness could not be made thin, the method of coating with a fluororesin could not be used for an extremely sharp blade such as a razor. In addition, other resin coatings also have a problem that adhesion strength is weak and there is a problem in durability. This is because the adhesive force with the blade substrate is due to physical adsorption. Further, the above-mentioned Japanese Patent Laid-Open No. 2-248480
Report, JP-A-60-40254 and JP-A-58-1
Japanese Patent No. 47483 also proposes a film thickness of nanometer level.
It was difficult to form carbon monoxide-based monolayers
The problem is that it could not be applied to blades and needles
was there.
【０００５】本発明は、前記従来技術の課題を解決する
ため、単分子膜からなるコーティング材料と基材とを化
学結合させることにより、刃物においては切れ味を鋭く
保ったままで切り屑が付着せず、針においては差し込み
抵抗が低く、しかも全体として防錆効果の高い単分子コ
ーティング物体を提供することを目的とする。In order to solve the above-mentioned problems of the prior art, the present invention chemically bonds a coating material composed of a monomolecular film to a base material, so that the cutting edge does not adhere to chips while the sharpness is kept sharp. The purpose of the present invention is to provide a single-molecule coated object which has a low insertion resistance in a needle and a high rust preventive effect as a whole.
【０００６】[0006]
【課題を解決するための手段】前記目的を達成するた
め、本発明の単分子コーティング物体は、刃物または針
基材の表面にコーティング膜が形成されてなる物体であ
って、前記基材が金属、セラミックスまたはプラスチッ
クからなり、その表面に厚さがナノメーターレベルのフ
ッ素を含む化学吸着単分子膜が、基材と化学結合によっ
て形成されていることを特徴とする。In order to achieve the above object, the monomolecular coated article of the present invention is an article in which a coating film is formed on the surface of a knife or needle substrate, and the substrate is a metal. A chemical adsorption monomolecular film made of ceramics or plastics and containing fluorine having a thickness of nanometer level is formed on the surface by a chemical bond with a base material.
【０００７】前記構成においては、フッ素を含む化学吸
着単分子膜が、少なくともシロキサン系単分子膜を介し
て形成されていることが好ましい。In the above structure, it is preferable that the chemisorption monomolecular film containing fluorine is formed at least via the siloxane monomolecular film.
【０００８】前記構成においては、刃物としては、包
丁、鋏、ナイフ、カッター、彫刻刀、剃刀、バリカン、
鋸、カンナ、ノミ、錐、千枚通し、バイト、ドリルの
刃、ミキサーの刃、ジュ−サ−の刃、製粉機の刃、芝刈
り機の刃、パンチ、押切り、ホッチキスの刃、缶切りの
刃、または手術用メスが例示される。また針としては、
鍼術用の針、縫い針、ミシン針、畳針、注射針、手術用
針、安全ピン等が例示される。In the above construction, the blades include knives, scissors, knives, cutters, chisels, razors, hair clippers,
Saw, canna, chisel, drill, awl, bite, drill blade, mixer blade, cutter blade, miller blade, lawn mower blade, punch, pusher, stapler blade, can opener blade , Or a surgical knife. As a needle,
Acupuncture needles, sewing needles, sewing needles, tatami needles, injection needles, surgical needles, safety pins and the like are exemplified.
【０００９】次に本発明方法の第１番目は、基材を洗浄
した後、一端にクロルシラン基（ＳｉＣｌn Ｘ3-n 基、
ただしｎ＝１，２，３、Ｘは官能基）を有し、他の一端
にフッ化炭素基を有するクロロシラン系界面活性剤を溶
かした非水系有機溶媒と前記基材表面とを接触させ脱塩
酸反応により、前記活性剤よりなる厚さがナノメーター
レベルの化学吸着単分子膜を基材表面全体に亘り形成す
る工程を含む単分子コーティング物体の製造方法であ
る。Next, the first of the methods of the present invention is to wash a substrate and then, at one end, chlorosilane group (SiCl n X 3-n group,
However, n = 1, 2, 3, X is a functional group, and the non-aqueous organic solvent in which a chlorosilane-based surfactant having a fluorocarbon group is dissolved at the other end is brought into contact with the surface of the substrate to remove the solvent. salt
Due to the acid reaction , the thickness of the activator is nanometer.
A method for producing a monomolecular coated object, which comprises the step of forming a high- level chemisorption monomolecular film over the entire surface of a substrate.
【００１０】次に本発明方法の第２番目は、基材を洗浄
した後、クロロシリル基を複数個含む物質を混ぜた非水
系溶媒に接触させて前記基材表面の水酸基と前記クロロ
シリル基を複数個含む物質のクロロシリル基とを反応さ
せて前記物質を前記基材表面に析出させる工程と、非水
系有機溶媒を用い前記基材上に残った余分なクロロシリ
ル基を複数個含む物質を洗浄除去した後、水と反応させ
て、前記基材上にシラノール基を複数個含む物質よりな
る単分子膜を形成する工程と、一端にクロルシラン基
（ＳｉＣｌn Ｘ3-n 基、ただしｎ＝１，２，３、Ｘは官
能基）を有し他の一端に直鎖状フッ化炭素基を含むクロ
ロシラン系界面活性剤を溶かした非水系有機溶媒と前記
単分子内層膜表面とを接触させ脱塩酸反応により、前記
活性剤よりなる厚さがナノメーターレベルの化学吸着単
分子膜を累積する工程とを含む単分子コーティング物体
の製造方法である。Next, in the second method of the present invention, after washing the substrate, the substrate is brought into contact with a non-aqueous solvent mixed with a substance containing a plurality of chlorosilyl groups so that the hydroxyl groups on the surface of the substrate and a plurality of the chlorosilyl groups are pluralized. A step of causing the substance to react with a chlorosilyl group of the substance to be deposited on the surface of the base material, and washing and removing a substance containing a plurality of extra chlorosilyl groups remaining on the base material using a non-aqueous organic solvent. Then, a step of reacting with water to form a monomolecular film made of a substance containing a plurality of silanol groups on the substrate, and a chlorosilane group (SiCl n X 3-n group, n = 1, 2, , 3, and X are functional groups) and a non-aqueous organic solvent in which a chlorosilane-based surfactant containing a linear fluorocarbon group at the other end is dissolved,
By contacting with the surface of the monomolecular inner layer film and dehydrochlorination reaction,
And a step of accumulating a chemisorption monomolecular film having a thickness of nanometer made of an activator .
【００１１】前記両製造方法において、一端にクロルシ
ラン基を有し他の一端に直鎖状フッ化炭素基を含むクロ
ロシラン系界面活性剤としては、ＣＦ3 −（ＣＦ2 ）n
−Ｒ−ＳｉＸp Ｃｌ3-p （ただしｎは０または整数、Ｒ
はアルキル基，エチレン基、アセチレン基，Ｓｉまたは
酸素原子を含む置換基を表わすがなくとも良い、ＸはＨ
またはアルキル基，シクロアルキル基，またはアリル基
の置換基、ｐは０，１または２）を用いることが好まし
い。In both of the above production methods, a chlorosilane-based surfactant having a chlorosilane group at one end and a linear fluorocarbon group at the other end is CF 3- (CF 2 ) n
-R-SiX p Cl 3-p (where n is 0 or an integer, R
Represents an alkyl group, an ethylene group, an acetylene group, a substituent containing Si or an oxygen atom, and is not necessary, X is H
Alternatively, it is preferable to use a substituent of an alkyl group, a cycloalkyl group, or an allyl group, and p is 0, 1 or 2).
【００１２】また、前記第２番目の製造方法において、
前工程で用いるクロロシリル基を複数個含む物質として
は、ＳｉＣｌ4 、またはＳｉＨＣｌ3 、ＳｉＨ2 Ｃ
ｌ2 、Ｃｌ−（ＳｉＣｌ2 Ｏ）n −ＳｉＣｌ3 （ただし
ｎは整数）を用いることが好ましい。In the second manufacturing method,
As the substance containing a plurality of chlorosilyl groups used in the previous step, SiCl 4 , SiHCl 3 , SiH 2 C
It is preferable to use l 2 , Cl- (SiCl 2 O) n -SiCl 3 (where n is an integer).
【００１３】[0013]
【作用】本発明においては、きわめて薄いナノメートル
（ｎｍ）レベルの膜厚のフッ化炭素系単分子膜を、刃物
または針基材の表面に基材と化学結合により形成するた
め、刃物の場合は本来の切れ味を損なうことなく、切り
屑の付着を防止でき、またフッ化炭素系単分子膜は撥水
撥油性にも優れているため防錆効果もある。従って、き
わめて切れ味が鋭く、切り屑が付着しなく、しかも防錆
効果の高い単分子コーティング物体とすることができ
る。また針の場合は差し込み抵抗が低くなり、しかも防
錆効果の高い単分子コーティング物体とすることができ
る。In the present invention, since a fluorocarbon-based monomolecular film having an extremely thin film thickness of nanometer (nm) level is formed on the surface of the blade or needle base material by chemical bonding with the base material, Can prevent the adhesion of chips without impairing the original sharpness, and since the fluorocarbon monomolecular film is also excellent in water and oil repellency, it also has a rust preventive effect. Therefore, it is possible to obtain a monomolecular-coated article which is extremely sharp, has no chips attached, and has a high rust preventive effect. Further, in the case of a needle, the insertion resistance is low, and a monomolecular coated article having a high rust preventive effect can be obtained.
【００１４】また本発明方法は、前記単分子コーティン
グ物体を合理的に効率よく製造することができる。Further, the method of the present invention can reasonably and efficiently manufacture the monomolecular coated article.
【００１５】[0015]
【実施例】一般の刃物は、通常鉄、ステンレス等の金属
やセラミックスでできており、針はスチール、銀、白金
などの金属でできているため、表面に水酸基（−ＯＨ
基）を含む。そこで、一端にクロルシラン基（ＳｉＣｌ
n Ｘ3-n 基、ｎ＝１，２，または３、Ｘは官能基）を有
する直鎖状炭素鎖を含む分子、例えばフッ化炭素基及び
クロロシラン基を含むクロロシラン系界面活性剤を混ぜ
た非水系溶媒に接触させて前記刃物や針の基材表面の水
酸基と前記クロロシリル基を複数個含む物質のクロロシ
リル基を反応させて前記物質よりなる単分子膜を前記基
材表面に析出させる、あるいはクロロシリル基を複数個
含む物質を混ぜた非水系溶媒に接触させて前記基材表面
の水酸基と前記クロロシリル基を複数個含む物質のクロ
ロシリル基を反応させて前記物質を前記基材表面に析出
させる工程と、非水系有機溶媒を用い前記基材表面に残
った余分なクロロシリル基を複数個含む物質を洗浄除去
し、前記基材上にクロロシリル基を複数個含む物質より
なるシロキサン系単分子膜を形成する工程と、一端にク
ロルシラン基を有する直鎖状炭素鎖を含むシラン系界面
活性剤を基材上に化学吸着し単分子吸着膜を累積する工
程とにより基材表面にフッ化炭素系化学吸着単分子累積
膜を製造できる。[Embodiment] A general cutting tool is usually made of metal such as iron or stainless steel or ceramics, and a needle is made of metal such as steel, silver or platinum.
Group) is included. Therefore, a chlorosilane group (SiCl
A molecule containing a linear carbon chain having n X 3-n group, n = 1, 2, or 3, X is a functional group, for example, a chlorosilane-based surfactant containing a fluorocarbon group and a chlorosilane group is mixed. By contacting with a non-aqueous solvent to react the chlorosilyl group of a substance containing a plurality of the chlorosilyl groups with hydroxyl groups on the substrate surface of the blade or needle to deposit a monomolecular film of the substance on the substrate surface, or Contacting a non-aqueous solvent mixed with a substance containing a plurality of chlorosilyl groups to react the hydroxyl groups on the surface of the substrate with the chlorosilyl groups of the substance containing a plurality of chlorosilyl groups to deposit the substance on the surface of the substrate And a substance containing a plurality of extra chlorosilyl groups remaining on the surface of the substrate using a non-aqueous organic solvent to be removed by washing, and a siloxane-based monolayer consisting of a substance containing a plurality of chlorosilyl groups on the substrate. Fluorination on the surface of the substrate by the step of forming a child film and the step of accumulating a monomolecular adsorption film by chemically adsorbing a silane-based surfactant containing a linear carbon chain having a chlorosilane group at one end on the substrate. A carbon-based chemisorption monomolecular cumulative film can be manufactured.
【００１６】以下に本発明に関する刃物として、包丁、
または鋏、ナイフ、カッター、彫刻刀、剃刀、バリカ
ン、鋸、カンナ、ノミ、錐、千枚通し、バイト、ドリル
の刃、ミキサーの刃、ジュ−サ−の刃、製粉機の刃、芝
かり機の刃、パンチ、押切り、ホッチキスの刃、缶切り
の刃、メス等があり、また針としては鍼術用の針、縫い
針、ミシン針、畳針、注射針、手術用針、安全ピン等が
あるが、代表例として包丁、鍼術用の針及び注射針を取
り上げ順に説明する。[0016] The following is a knife relating to the present invention, a kitchen knife,
Or scissors, knife, cutter, chisel, razor, hair clipper, saw, canna, chisel, awl, awl, bite, drill blade, mixer blade, juicer blade, miller blade, lawn mower There are blades, punches, pressers, stapler blades, can opener blades, scalpels, etc., and needles include acupuncture needles, sewing needles, sewing needles, tatami needles, injection needles, surgical needles, safety pins, etc. However, as a typical example, a kitchen knife, an acupuncture needle, and an injection needle will be described in order.
【００１７】以下具体例を説明するが、本発明は下記の
実施例に限定されるものではない。Specific examples will be described below, but the present invention is not limited to the following examples.
【００１８】実施例１ まず、研磨の終了したスチール製の包丁を用意し、有機
溶媒でよく洗浄した後、フッ化炭素基及びクロロシラン
基を含む物質を混ぜた非水系の溶媒、例えば、ＣＦ
3 （ＣＦ2 ）7 （ＣＨ2 ）2 ＳｉＣｌ3 を用い、１重量
％程度の濃度で溶かした８０重量％ｎ−ヘキサデカン
（トルエン、キシレン、ジシクロヘキシルでもよい）、
１２重量％四塩化炭素、８重量％クロロホルム溶液を調
整し、前記包丁を２時間程度浸漬すると、スチール包丁
（セラミック刃物でも同じ）の表面は自然酸化膜が形成
されており、その酸化膜表面には水酸基が多数含まれて
いるので、フッ化炭素基及びクロロシラン基を含む物質
のＳｉＣｌ基と前記水酸基が反応し脱塩酸反応が生じ包
丁表面全面にわたり、ＣＦ3 （ＣＦ2 ）7 （ＣＨ2 ）2
Ｓｉ（Ｏ−）3 の結合が生成され、図１に示すフッ素を
含む単分子膜２が包丁の基材１の表面と化学結合した状
態で約１５オングストローム（１．５ｎｍ）の膜厚で形
成できた。なお、単分子膜は碁番目試験を行なっても全
く剥離することがなかった。Example 1 First, a steel knife after polishing was prepared, washed thoroughly with an organic solvent, and then a non-aqueous solvent, for example, CF, mixed with a substance containing a fluorocarbon group and a chlorosilane group.
80% by weight n-hexadecane (toluene, xylene, dicyclohexyl may be used) dissolved in a concentration of about 1% by weight using 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 .
When a 12 wt % carbon tetrachloride and 8 wt % chloroform solution was prepared and the kitchen knife was immersed for about 2 hours, a natural oxide film was formed on the surface of the steel knife (ceramic knife as well). Since a large number of hydroxyl groups are contained, the SiCl group of a substance containing a fluorocarbon group and a chlorosilane group reacts with the hydroxyl groups to cause a dehydrochlorination reaction, and CF 3 (CF 2 ) 7 (CH 2 ) 2
The Si (O-) 3 bond is generated, and the fluorine-containing monomolecular film 2 shown in FIG. 1 is chemically bonded to the surface of the base material 1 of the kitchen knife to have a thickness of about 15 Å (1.5 nm). did it. In addition, the monomolecular film did not peel at all even when the go test was performed.
【００１９】この包丁で、食パンを切ってみたが、パン
屑は殆ど付着せず、きわめてきれいな断面が得られた。
また、巻寿司を切った場合には、飯粒は全く付着せずき
わめてきれいな断面が得られた。また、この包丁を水に
つけ込んで置いたが、全く錆を生じなかった。さらにま
た、剃刀の刃に単分子膜を吸着し、髭を剃ってみたが、
きわめて滑らかな切れ味であった。I tried to cut a loaf of bread with this kitchen knife, but bread crumbs hardly adhered and a very clean cross section was obtained.
In addition, when sushi rolls were cut, rice grains did not adhere at all and a very clean cross section was obtained. Moreover, when this kitchen knife was immersed in water and placed, no rust occurred. Furthermore, I tried to shave my beard by adsorbing the monomolecular film on the blade of the razor,
It was extremely smooth.
【００２０】実施例２ 親水性ではあるが水酸基を含む割合が少ない包丁（Ａｌ
やＣｕ、ステンレス等の金属、表面を親水化したプラス
チック包丁（プラスチックの様な表面に酸化膜を持たな
い物質であれば、予め表面を酸素を含むプラズマ雰囲気
中で、例えば１００Ｗで２０分処理して親水化即ち表面
に水酸基を導入しておけばよい。）の場合、トリクロロ
シリル基を複数個含む物質［例えば、ＳｉＣｌ4 、また
はＳｉＨＣｌ3 、ＳｉＨ2 Ｃｌ2 、Ｃｌ−（ＳｉＣｌ2
Ｏ）n −ＳｉＣｌ3 （ｎは整数）。特に、ＳｉＣｌ4 を
用いれば、分子が小さく水酸基に対する活性も大きいの
で、包丁表面を均一に親水化する効果が大きい］を混ぜ
た非水系溶媒、例えばクロロホルム溶媒に１重量パーセ
ント溶解した溶液に３０分間程度浸漬すると、包丁１１
表面には親水性のＯＨ基１２が多少とも存在するので
（図２）、表面で脱塩酸反応が生じトリクロロシリル基
を複数個含む物質のクロロシラン単分子膜が形成され
る。Example 2 A kitchen knife (Al which is hydrophilic but has a small proportion of hydroxyl groups)
Metals such as Cu, stainless steel, etc., and plastic knives with a hydrophilic surface (for substances such as plastics that do not have an oxide film on the surface, the surface is pretreated in a plasma atmosphere containing oxygen, for example, at 100 W for 20 minutes. In the case of hydrophilization, that is, introduction of hydroxyl groups on the surface), a substance containing a plurality of trichlorosilyl groups [for example, SiCl 4 , or SiHCl 3 , SiH 2 Cl 2 , Cl- (SiCl 2
O) n -SiCl 3 (n is an integer). In particular, if SiCl 4 is used, the molecule is small and the activity against hydroxyl groups is large, so the effect of making the surface of the kitchen knife hydrophilic is great] is mixed for 30 minutes in a solution of 1 wt% dissolved in a non-aqueous solvent such as chloroform solvent. A knife 11
Since there are some hydrophilic OH groups 12 on the surface (FIG. 2), dehydrochlorination reaction occurs on the surface and a chlorosilane monomolecular film of a substance containing a plurality of trichlorosilyl groups is formed.
【００２１】例えば、トリクロロシリル基を複数個含む
物質としてＳｉＣｌ4 を用いれば、包丁１１表面には少
量の親水性のＯＨ基が露出されているので、表面で脱塩
酸反応が生じ、Ｓｉ（Ｃｌ）3 Ｏ− や −ＯＳｉ（Ｃ
ｌ）2 Ｏ−のように分子が−ＳｉＯ−結合を介して表面
に固定される。For example, if SiCl 4 is used as a substance containing a plurality of trichlorosilyl groups, a small amount of hydrophilic OH groups are exposed on the surface of the kitchen knife 11, so that a dehydrochlorination reaction occurs on the surface and Si (Cl ) 3 O- and -OSi (C
l) Molecules, such as 2 O-, are immobilized on the surface via -SiO- bonds.
【００２２】その後、非水系の溶媒例えばクロロホルム
で洗浄して、さらに水で洗浄すると、包丁と反応してい
ないＳｉＣｌ4 分子は除去され、包丁表面にＳｉ（Ｏ
Ｈ）3Ｏ− や −ＯＳｉ（ＯＨ）2 Ｏ−等のシロキサ
ン単分子膜１３が得られる（図３）。After that, washing with a non-aqueous solvent such as chloroform and further washing with water removes SiCl 4 molecules which have not reacted with the knife, and the Si (O
H) 3 O-or -OSi (OH) 2 O-such as siloxane monomolecular film 13 is obtained (FIG. 3).
【００２３】なお、このときできた単分子膜１３は包丁
とは−ＳｉＯ−の化学結合を介して完全に結合されてい
るので、分解反応などがない限り剥がれることが無い。
また、得られた単分子膜は表面にＳｉＯＨ結合を数多く
持つ。当初の水酸基の約３倍程度の数が生成される。Since the monomolecular film 13 formed at this time is completely bonded to the kitchen knife through a chemical bond of -SiO-, it does not peel off unless there is a decomposition reaction or the like.
The obtained monomolecular film has many SiOH bonds on the surface. About three times as many as the initial hydroxyl groups are generated.
【００２４】そこでさらに、フッ化炭素基及びクロロシ
ラン基を含む物質を混ぜた非水系の溶媒、例えば、ＣＦ
3 （ＣＦ2 ）7 （ＣＨ2 ）2 ＳｉＣｌ3 を用い、１重量
％程度の濃度で溶かした８０重量％ｎ−ヘキサデカン、
１２重量％四塩化炭素、８重量％クロロホルム溶液を調
整し、前記表面にＳｉＯＨ結合を数多く持つ単分子膜の
形成された包丁を１時間程度浸漬すると、包丁表面にＣ
Ｆ3 （ＣＦ2 ）7 （ＣＨ2 ）2 Ｓｉ（Ｏ−）3 の結合が
生成され、フッ素を含む単分子膜１４が下層のシロキサ
ン単分子膜と化学結合した状態で包丁全面に亘り約２０
オングストローム（２．０ｎｍ）の膜厚で形成できた
（図４）。なお、単分子膜は碁番目試験を行なっても全
く剥離することがなかった。Therefore, a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group, for example, CF
80% by weight n-hexadecane dissolved at a concentration of about 1% by weight using 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 .
A 12 wt % carbon tetrachloride, 8 wt % chloroform solution was prepared, and a knife with a monomolecular film having a large number of SiOH bonds formed on the surface was immersed for about 1 hour.
F 3 (CF 2) 7 ( CH 2) 2 Si (O-) 3 bond is produced, about 20 over the knife entirely in a state of monomolecular film 14 is chemically bonded to the lower layer of the siloxane monomolecular film containing fluorine
It could be formed with a film thickness of angstrom (2.0 nm) (FIG. 4). In addition, the monomolecular film did not peel at all even when the go test was performed.
【００２５】さらにまた、上記実施例では、フッ化炭素
系界面活性剤としてＣＦ3 （ＣＦ2）7 （ＣＨ2 ）2 Ｓ
ｉＣｌ3 を用いたが、アルキル鎖部分にエチレン基やア
セチレン基を付加したり組み込んでおけば、単分子膜形
成後５メガラド程度の電子線照射で架橋できるのでさら
に単分子膜の硬度を向上させることも可能である。Furthermore, in the above embodiment, CF 3 (CF 2 ) 7 (CH 2 ) 2 S is used as the fluorocarbon surfactant.
Although iCl 3 was used, by adding or incorporating an ethylene group or an acetylene group in the alkyl chain portion, it is possible to crosslink by electron beam irradiation of about 5 megarads after forming the monomolecular film, so that the hardness of the monomolecular film is further improved. It is also possible.
【００２６】なお、フッ化炭素系界面活性剤として上記
のもの以外にもＣＦ3 ＣＨ2 Ｏ（ＣＨ2 ）15ＳｉＣ
ｌ3 、ＣＦ3 （ＣＨ2 ）2 Ｓｉ（ＣＨ3 ）2 （ＣＨ2 ）
15ＳｉＣｌ3 、Ｆ（ＣＦ2 ）8 （ＣＨ2 ）2 Ｓｉ（ＣＨ
3 ）2 （ＣＨ2 ）9 ＳｉＣｌ3 、ＣＦ3 ＣＯＯ（Ｃ
Ｈ2 ）15ＳｉＣｌ3 等が利用できる。In addition to the above-mentioned fluorocarbon surfactants, CF 3 CH 2 O (CH 2 ) 15 SiC is used.
l 3 , CF 3 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 )
15 SiCl 3 , F (CF 2 ) 8 (CH 2 ) 2 Si (CH
3 ) 2 (CH 2 ) 9 SiCl 3 , CF 3 COO (C
H 2 ) 15 SiCl 3 or the like can be used.
【００２７】以上の実施例から明らかな通り、一般の刃
物は、通常金属やセラミクスでできているため、表面に
水酸基（−ＯＨ基）を含む。そこで、一端にクロルシラ
ン基（ＳｉＣｌn Ｘ3-n 基、ｎ＝１，２，または３、Ｘ
は官能基）を有する直鎖状炭素鎖を含む分子、例えばフ
ッ化炭素基及びクロロシラン基を含むクロロシラン系界
面活性剤を混ぜた非水系溶媒に接触させて前記刃物表面
の水酸基と前記クロロシリル基を複数個含む物質のクロ
ロシリル基を反応させて前記物質よりなる単分子膜を前
記刃物表面に析出させる、あるいはクロロシリル基を複
数個含む物質を混ぜた非水系溶媒に接触させて前記刃物
表面の水酸基と前記クロロシリル基を複数個含む物質の
クロロシリル基を反応させて前記物質を前記刃物表面に
析出させる工程と、非水系有機溶媒を用い前記刃物表面
に残った余分なクロロシリル基を複数個含む物質を洗浄
除去し、前記刃物上にクロロシリル基を複数個含む物質
よりなるシロキサン系単分子膜を形成する工程と、一端
にクロルシラン基を有する直鎖状炭素鎖を含むシラン系
界面活性剤を刃物上に化学吸着し単分子吸着膜を累積す
る工程とにより刃物表面にフッ化炭素系化学吸着単分子
累積膜を製造できる。As is clear from the above examples, since a general blade is usually made of metal or ceramics, its surface contains a hydroxyl group (—OH group). Therefore, at one end, a chlorosilane group (SiCl n X 3-n group, n = 1, 2, or 3, X
Is a molecule containing a linear carbon chain having a functional group), for example, a non-aqueous solvent mixed with a chlorosilane-based surfactant containing a fluorocarbon group and a chlorosilane group is brought into contact with the hydroxyl group on the surface of the blade and the chlorosilyl group. A chlorosilyl group of a plurality of substances is reacted to deposit a monolayer of the substance on the blade surface, or a hydroxyl group on the blade surface is brought into contact with a non-aqueous solvent mixed with a substance containing a plurality of chlorosilyl groups. A step of reacting chlorosilyl groups of a substance containing a plurality of chlorosilyl groups to deposit the substance on the surface of the blade, and washing a substance containing a plurality of excess chlorosilyl groups remaining on the surface of the blade using a non-aqueous organic solvent A step of removing and forming a siloxane-based monomolecular film made of a substance containing a plurality of chlorosilyl groups on the blade, and a chlorosilane group at one end A silane-based surfactant comprising linear carbon chain can be produced fluorocarbon chemisorption monomolecular film on the tool surface by a step of accumulating a chemically adsorbed monomolecular adsorbed film on a tool having.
【００２８】実施例３ 研磨の終了したスチール製の鍼術用の針、及び注射針を
用意し、有機溶媒で洗浄した後実施例１と同様に処理し
て単分子膜を形成した。単分子膜の厚さは約１５オング
ストロームであった。この針は表面の滑り性が優れてい
た。この針で鍼術師に鍼術試験をしてもらったところ、
刺し込み圧が低いという評価を得た。また注射針による
注射では、処理しないものに比べて大幅に痛みを和らげ
ることができた。また、これらの針を水につけ込んでお
いたが錆は生じなかった。さらに単分子膜は基材表面と
強固に化学結合しており、剥離などの問題は生じなかっ
た。同様にミシン針に本発明の単分子膜を形成したとこ
ろ、針の摩擦抵抗が減少し縫製性に優れたものとなっ
た。Example 3 A polished acupuncture needle made of steel and an injection needle were prepared, washed with an organic solvent and treated in the same manner as in Example 1 to form a monomolecular film. The monolayer thickness was about 15 Å. This needle had excellent surface slipperiness. When I got an acupuncturist to do an acupuncture test with this needle,
It was evaluated that the piercing pressure was low. In addition, injection with a needle was able to relieve much more pain than that without treatment. Also, these needles were immersed in water, but no rust occurred. Further, the monomolecular film was strongly chemically bonded to the surface of the base material, and no problems such as peeling occurred. Similarly, when the monomolecular film of the present invention was formed on the sewing machine needle, the frictional resistance of the needle was reduced and the sewing property was excellent.
【００２９】[0029]
【発明の効果】以上述べてきたように、きわめて薄いナ
ノメータレベルの膜厚のフッ化炭素系単分子膜を刃物表
面に全面形成するため、刃物本来の切れ味を損なうこと
なく、切り屑の付着を防止でき、またフッ化炭素系単分
子膜は撥水撥油性にも優れているため防錆効果もある。
従って、きわめて切れ味が鋭く、切り屑が付着しなく、
しかも防錆効果の高い単分子コーティング物体を提供で
きる。また針の場合も、表面の滑り性が向上して刺し込
み圧が低く痛みを和らげることができ、また錆の発生も
防止できる。As described above, since the fluorocarbon-based monomolecular film having an extremely thin nanometer level film is formed on the entire surface of the blade, it is possible to prevent chips from adhering without impairing the original blade sharpness. In addition, since the fluorocarbon monolayer is excellent in water repellency and oil repellency, it also has a rust preventive effect.
Therefore, it is extremely sharp and does not adhere to chips,
Moreover, it is possible to provide a monomolecular coated object having a high rust prevention effect. Also in the case of a needle, the slipperiness of the surface is improved, the puncture pressure is low, pain can be relieved, and rust can also be prevented.
【図１】本発明の単分子コーティング物体の代表的な例
である刃物としての包丁の表面を分子レベルまで拡大し
た断面概念図である。FIG. 1 is a conceptual cross-sectional view in which the surface of a knife, which is a typical example of a monomolecular coated object of the present invention, is enlarged to a molecular level.
【図２】本発明の刃物の第２実施例を説明するためのコ
ーティング処理前の刃物基材を分子レベルまで拡大した
表面断面概念図。FIG. 2 is a conceptual sectional view of a surface of a blade substrate before coating, which is enlarged to a molecular level, for explaining a second embodiment of the blade of the present invention.
【図３】本発明の刃物の第２の実施例を説明するための
包丁の基材表面を分子レベルまで拡大した断面の中間工
程概念図である。FIG. 3 is a conceptual diagram of an intermediate step of a cross-section in which a base material surface of a kitchen knife is enlarged to a molecular level for explaining a second embodiment of a cutting tool of the present invention.
【図４】本発明の刃物の第２の実施例を説明するための
コーティングの終了した包丁の基材表面を分子レベルま
で拡大した断面工程概念図である。FIG. 4 is a sectional process conceptual diagram in which the surface of a base material of a knife after coating has been enlarged to a molecular level for explaining a second embodiment of a cutting tool of the present invention.
【符号の説明】 １，１１…刃物基材、 ２，１４…単
分子膜、 １３…シロキサン単分子内層膜。[Explanation of Codes] 1,11 ... Blade base material, 2, 14 ... Monomolecular film, 13 ... Siloxane monomolecular inner layer film.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ａ６１Ｂ 17/06 Ａ６１Ｂ 17/06 (56)参考文献 特開 平２−248480（ＪＰ，Ａ) 特開 昭60−40254（ＪＰ，Ａ) 特開 昭58−147483（ＪＰ，Ａ)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location // A61B 17/06 A61B 17/06 (56) References JP-A-2-248480 (JP, A ) JP-A-60-40254 (JP, A) JP-A-58-147483 (JP, A)
Claims (7)
膜が形成されてなる物体であって、前記基材が金属、セ
ラミックスまたはプラスチックからなり、その表面に厚
さがナノメーターレベルのフッ素を含む化学吸着単分子
膜が基材と化学結合によって形成されていることを特徴
とする単分子コーティング物体。1. An object in which a coating film is formed on the surface of a knife or a needle base material, wherein the base material is made of metal, ceramics or plastic, and the thickness of the surface is large.
A monomolecular coated object, wherein a chemisorption monomolecular film containing fluorine at a nanometer level is formed by chemical bonding with a substrate.
くともシロキサン系単分子膜を介して形成されている請
求項１記載の単分子コーティング物体。2. The monomolecular coated article according to claim 1, wherein the chemisorption monomolecular film containing fluorine is formed at least through the siloxane monomolecular film.
彫刻刀、剃刀、バリカン、鋸、カンナ、ノミ、錐、千枚
通し、バイト、ドリルの刃、ミキサーの刃、ジュ−サ−
の刃、製粉機の刃、芝刈り機の刃、パンチ、押切り、ホ
ッチキスの刃、缶切りの刃、または手術用メスから選ば
れる刃物、または鍼術用の針、縫い針、ミシン針、畳
針、注射針、手術用針、安全ピンから選ばれる針である
請求項１または２記載の単分子コーティング物体。3. The base material is a kitchen knife, scissors, knife, cutter,
Chisel, razor, hair clipper, saw, planer, chisel, awl, awl, bite, drill blade, mixer blade, juicer
Blades, miller blades, lawn mower blades, punches, pushers, stapler blades, can opener blades, or blades selected from surgical scalpels, or needles for acupuncture, sewing needles, sewing needles, tatami mats The monomolecular coated object according to claim 1 or 2, which is a needle selected from a needle, an injection needle, a surgical needle, and a safety pin.
基（ＳｉＣｌn Ｘ3-n基、ただしｎ＝１，２，３、Ｘは
官能基）を有し、他の一端にフッ化炭素基を有するクロ
ロシラン系界面活性剤を溶かした非水系有機溶媒と前記
基材表面とを接触させ脱塩酸反応により、前記活性剤よ
りなる厚さがナノメーターレベルの化学吸着単分子膜を
基材表面全体に亘り形成する工程を含む単分子コーティ
ング物体の製造方法。4. After washing the base material, it has a chlorosilane group (SiCl n X 3-n group, where n = 1, 2, 3, X is a functional group) at one end and fluorocarbon at the other end. A non-aqueous organic solvent in which a chlorosilane-based surfactant having a group is dissolved, and
A method for producing a monomolecular coated object, comprising the step of forming a chemisorption monomolecular film of the above-mentioned activator having a thickness of nanometer over the entire surface of the base material by bringing it into contact with the surface of the base material and performing a dehydrochlorination reaction .
数個含む物質を混ぜた非水系溶媒に接触させて前記基材
表面の水酸基と前記クロロシリル基を複数個含む物質の
クロロシリル基とを反応させて前記物質を前記基材表面
に析出させる工程と、非水系有機溶媒を用い前記基材上
に残った余分なクロロシリル基を複数個含む物質を洗浄
除去した後、水と反応させて、前記基材上にシラノール
基を複数個含む物質よりなる単分子内層膜を形成する工
程と、一端にクロルシラン基（ＳｉＣｌn Ｘ3-n 基、た
だしｎ＝１，２，３、Ｘは官能基）を有し他の一端に直
鎖状フッ化炭素基を含むクロロシラン系界面活性剤を溶
かした非水系有機溶媒と前 記単分子内層膜表面とを接触
させ脱塩酸反応により、前記活性剤よりなる厚さがナノ
メーターレベルの化学吸着単分子膜を累積する工程とを
含む単分子コーティング物体の製造方法。5. After washing the substrate, the substrate is contacted with a non-aqueous solvent mixed with a substance containing a plurality of chlorosilyl groups to react the hydroxyl groups on the surface of the substrate with the chlorosilyl groups of the substance containing a plurality of chlorosilyl groups. And then depositing the substance on the surface of the base material, and washing and removing a substance containing a plurality of excess chlorosilyl groups remaining on the base material using a non-aqueous organic solvent, and then reacting with water to A step of forming a monomolecular inner layer film made of a substance containing a plurality of silanol groups on a substrate, and a chlorosilane group (SiCl n X 3-n group, where n = 1, 2, 3, X is a functional group) at one end soluble chlorosilane-based surface active agent containing a linear fluorocarbon group on the other end have a
Contacting however was a non-aqueous organic solvent and before Symbol monomolecular inner layer film surface
By the dehydrochlorination reaction, the thickness of the activator becomes nano
A method of manufacturing a monomolecular coated object, comprising: accumulating a chemisorption monomolecular film at a meter level .
ＳｉＣｌ4 、またはＳｉＨＣｌ3 、ＳｉＨ2 Ｃｌ2 、Ｃ
ｌ−（ＳｉＣｌ2 Ｏ）n −ＳｉＣｌ3 （ただしｎは整
数）を用いる請求項５記載の単分子コーティング物体の
製造方法。6. The substance containing a plurality of chlorosilyl groups is SiCl 4 , or SiHCl 3 , SiH 2 Cl 2 , C.
The method for producing a monomolecular coated article according to claim 5, wherein l- (SiCl 2 O) n -SiCl 3 (where n is an integer) is used.
直鎖状フッ化炭素基を含むクロロシラン系界面活性剤と
してＣＦ3 −（ＣＦ2 ）n −Ｒ−ＳｉＸp Ｃｌ3-p （た
だしｎは０または整数、Ｒはアルキル基，エチレン基、
アセチレン基，Ｓｉまたは酸素原子を含む置換基を表わ
すがなくとも良い、ＸはＨまたはアルキル基，シクロア
ルキル基，またはアリル基の置換基、ｐは０，１または
２）を用いる請求項４または５記載の単分子コーティン
グ物体の製造方法。7. CF 3 to the other end having a chlorosilane group at one end as a chlorosilane-based surface active agent containing a linear fluorocarbon group - (CF 2) n -R- SiX p Cl 3-p ( provided that n is 0 or an integer, R is an alkyl group, an ethylene group,
An acetylene group, Si or a substituent containing an oxygen atom may or may not be represented, X is H or a substituent of an alkyl group, a cycloalkyl group, or an allyl group, and p is 0, 1 or 2). 5. The method for producing a monomolecular coated article according to item 5.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3024025A JP2501248B2 (en) | 1991-01-23 | 1991-01-23 | Monomolecular coating object and method of manufacturing the same |
| CA 2054094 CA2054094C (en) | 1990-10-25 | 1991-10-23 | Chemically adsorbed monomolecular lamination film |
| DE1991622212 DE69122212T2 (en) | 1990-10-25 | 1991-10-23 | Monomolecular film laminated by chemical adsorption and process for its production |
| EP19910118094 EP0484746B1 (en) | 1990-10-25 | 1991-10-23 | Chemically adsorbed monomolecular lamination film and method of manufacturing the same |
| KR1019910018799A KR950004153B1 (en) | 1990-10-25 | 1991-10-25 | Chemically adsorbed monomolecular lamination film and method of manufacturing the same |
| US08/037,727 US5380585A (en) | 1990-10-25 | 1993-03-26 | Chemically adsorbed monomolecular lamination film |
| US08/316,105 US5466486A (en) | 1990-10-25 | 1994-09-30 | Chemically adsorbed monomolecular lamination film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3024025A JP2501248B2 (en) | 1991-01-23 | 1991-01-23 | Monomolecular coating object and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04239635A JPH04239635A (en) | 1992-08-27 |
| JP2501248B2 true JP2501248B2 (en) | 1996-05-29 |
Family
ID=12126991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3024025A Expired - Fee Related JP2501248B2 (en) | 1990-10-25 | 1991-01-23 | Monomolecular coating object and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2501248B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5854722A (en) | 1993-08-26 | 1998-12-29 | International Business Machines Corporation | Method and apparatus for rotary actuator arc compensation correction in a direct access storage device |
| US6002540A (en) | 1995-05-18 | 1999-12-14 | International Business Machines Corporation | Method and apparatus for rotary actuator arc compensation correction in a direct access storage device |
| US9373805B2 (en) | 2007-03-31 | 2016-06-21 | Empire Technology Development Llc | Optical sensor and method for making the same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2732777B2 (en) * | 1992-05-27 | 1998-03-30 | 松下電器産業株式会社 | Manufacturing method of chemisorption membrane |
| JP2000325355A (en) * | 1999-05-18 | 2000-11-28 | Nippon Acp Kk | Surgical knife |
| JP2007173518A (en) * | 2005-12-22 | 2007-07-05 | Kagawa Univ | Optical sensor and manufacturing method thereof |
| JP5374674B2 (en) * | 2007-03-31 | 2013-12-25 | 国立大学法人 香川大学 | Solar cell and method for manufacturing the same |
| JP5707578B2 (en) * | 2012-07-17 | 2015-04-30 | 株式会社新日本テック | Fluorine coating structure, coating object thereof and coating method thereof |
| JP6711489B2 (en) * | 2017-05-26 | 2020-06-17 | 株式会社フロロテクノロジー | Coating agent |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58147483A (en) * | 1982-02-26 | 1983-09-02 | Asahi Glass Co Ltd | Water and oil repellent for glass surface |
| JPS6040254A (en) * | 1983-08-16 | 1985-03-02 | 旭硝子株式会社 | Water-repellent oil-repellent film |
| JPH0781024B2 (en) * | 1989-03-22 | 1995-08-30 | 旭硝子株式会社 | Water repellency. Antifouling transparent base material and structure equipped with the same |
-
1991
- 1991-01-23 JP JP3024025A patent/JP2501248B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5854722A (en) | 1993-08-26 | 1998-12-29 | International Business Machines Corporation | Method and apparatus for rotary actuator arc compensation correction in a direct access storage device |
| US6002540A (en) | 1995-05-18 | 1999-12-14 | International Business Machines Corporation | Method and apparatus for rotary actuator arc compensation correction in a direct access storage device |
| US9373805B2 (en) | 2007-03-31 | 2016-06-21 | Empire Technology Development Llc | Optical sensor and method for making the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04239635A (en) | 1992-08-27 |
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